Ultraporous sol gel monoliths and methods for preparing the same are provided, having superior flow characteristics for chromatography and analytical chemistry applications. The methods for forming an ultra porous sol-gel monolith include (a) forming a solution comprising a porogen, a matrix dissolving catalyst and a sol gel precursor; (b) allowing the solution to form a gel; and (c) drying the gel at an elevated temperature. The ultraporous sol gel monoliths are characterized by a porosity of up to about 97%, a BET surface area of at least about 50 m.sup.2/g and substantially no micropores.